Stereoselectivity in Intramolecular Cyclization of Non-conjugated Unsaturated Ketones by Electroreduction

Abstract

This study showed some decrease in stereoselectivity in electroreductive intramolecular cyclization of nitrogen-containing non-conjugated enones in comparison with high stereoselectivity for the corresponding enones possessing an all-carbon-chain or a sulfur-containing chain. This phenomenon may provide some actual experimental supports for the remarkable stereochemical features of the electroreductive cyclization.

Some Progress and Development on Synthetic Electroorganic Chemistry

“…For example, electroreduction of activated olefins such as α,β-unsaturated esters, nitriles and ketones in the presence of acid anhydrides brought about regioselective C-acylation of the substrates to form the corresponding β-acylated products in good to excellent yields. 16)…”

Intramolecular reductive cyclisations using electrochemistry: development of environmentally friendly synthetic methodologies

“…Biologically active intermediates have been prepared from unsaturated nitrogen or sulfur derivatives. 131 For example, carbonyl compound 80 underwent a stereoselective reductive cyclisation to afford regioselectively the corresponding heterocyclic alcohols 81 in 90% yield (Scheme 41). 132 Highly stereoselective cyclisations of non-conjugated unsaturated ketones have been reported in direct electrolyses in DMF-2-propanol mixtures at a mercury cathode in the presence of N,N-methylquinuclidinium salts.…”